General chemistry

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GENERAL CHEMISTRY I
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CHAPTER ONE
INTRODUCTION TO ORGANIC CHEMISTRY
1.1 HISTORICAL BACKGROUND OF ORGANIC CHEMISTRY
Organic chemistry is the area of chemistry that involves the study of carbon and
its compounds. Carbon is now known to form a seemingly unlimited number of
compounds. The uses of organic compounds impact our lives daily in medicine,
agriculture, and general life.
In theory (Oparin, 1923) organic chemistry may have its beginnings with the big
bang when the components of ammonia, nitrogen, carbon dioxide and methane
combined to form amino acids, an experiment that has been verified in the
laboratory (Miller, 1950). Organic chemicals were used in ancient times by
Romans and Egyptians as dyes, medicines and poisons from natural sources, but
the chemical composition of the substances was unknown.
In the 16th century organic compounds were isolated from nature in the pure
state (Scheele, 1769) and analytical methods were developed for determination
of elemental composition (Lavoisier, 1784).
Scientists believed (Berzelius, 1807) that organic chemicals found in nature

contained a special "vital force" that directed their natural synthesis, and
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therefore, it would be impossible to accomplish a laboratory synthesis of the

chemicals.
Fortunately, later in the century Frederich Wöhler (1828) discovered that urea, a
natural component in urine, could be synthesized in the laboratory by heating
ammonium cyanate. His discovery meant that the natural "vital force" was not
required to synthesis organic compounds, and paved the way for many chemists
to synthesize organic compounds.
By the middle of the nineteenth century, many advances had been made into the
discovery, analysis and synthesis of many new organic compounds.
Understanding about the structures of organic chemistry began with a theory of
bonding called valence theory (Kekule, Couper, 1858).
Organic chemistry developed into a productive and exciting science in the

nineteenth century. Many new synthetic methods, reaction mechanisms,
analytical techniques and structural theories have been developed. Toward the
end of the century much of the knowledge of organic chemistry has been
expanded to the study of biological systems such as proteins and DNA. Volumes
of information are published monthly in journals, books and electronic media
about organic and biological chemistry.
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The vast information available today means that, for new students of organic
chemistry, a great deal of study is required. Students must learn about organic
reactions, mechanism, synthesis, analysis, and biological function.
The study of organic chemistry, although complex, is very interesting, and begins
here with an introduction of the theory of chemical bonding.
1.2 THE CHEMICAL BOND
1.2a Atomic Theory
The atomic theory of electrons began in the early 1900s and gained acceptance
around 1926 after Heisenberg and Schroedinger found mathematical solutions to
the electronic energy levels found in atoms, the field is now called quantum
mechanics.
Electrons exist in energy levels that surround the nucleus of the atom. The energy
of these levels increases as they get farther from the nucleus. The energy levels
are called shells, and within these shells are other energy levels, called subshells
or orbitals, that contain up to two electrons. The calculations from atomic theory
give the following results for electron energy and orbitals. The results for the first
two energy levels (shells 1 and 2) are the most important for bonding in organic
chemistry.
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Orbitals
Shell s p d f Total Electrons Possible
1 1 2
2 2 3 8
3 3 3 5 18 4 1 3 5 7 32
*energy level 1 contains up to two electrons in a spherical orbital called a 1s-

orbital.
*energy level 2 contains up to eight electrons; two in a2s-orbital and two in each
of three orbitals designated as 2p-orbitals. The p-orbitals have a barbell type
shape and are aligned along the x, y, and z axes. They are thus called the px, py,
and pz orbitals.
*energy level 3 contains up to eighteen electrons, two electrons in a 3s-orbital,
six electrons in the three 3p-orbitals, and ten electrons in the five 3d-orbitals.
*energy level 4 contains up to thirty-two electrons, two electrons in a 4s-orbital,

six electrons in the three 4p-orbitals, ten electrons in the five 4d-orbitals, and
fourteen electrons in the seven 4f-orbitals.
Electrons fill the lower energy levels first until all of the electrons are used
(Aufbau Principle). An element contains the number of electrons equal to its
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atomic number. For the first and second row elements the electron configurations
are relatively simple.
Element (atomic number) Electron Configuration
H (1) 1s1 (1st shell, s orbital, one electron)

He (2) 1s2
Li (3) 1s2, 2s1
Be (4) 1s2, 2s2
B (5) 1s2, 2s2, 2p1
C (6) 1s2, 2s2, 2p2
N (7) 1s2, 2s2, 2p3
O (8) 1s2, 2s2, 2p4
F (9) 1s2, 2s2, 2p5
Ne (10) 1s2, 2s2, 2p6 (inert, completely filled)
1.2b Electro negativity
Electronegativity is the ability of an atom to attract electrons to itself, and

generally increases as one moves from left to the right across the periodic table.
least mostelectronegative Li < Be < B < C < N < O < F electronegative
Electronegativity also increases as we go from the bottom to the top of a column

in the periodic table.
least most
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electronegative I < Br < Cl < F electronegative
Elements that easily lose electrons and attain a positive charge are called
electropositive elements. Alkali metals are electropositive elements.
1.2c Bonding
Atoms can become bonded with each other, and their electronic structure
governs the type of bond formed. The main two types of bonds that are formed
are called ionic and covalent.
Ionic Bond
Ionic bonding is important between atoms of vastly different electronegativity.

The bond results from one atom giving up an electron while another atom accepts
the electron. Both atoms attain a stable nobel gas configuration.
In the compound lithium fluoride, the 2s1 electron of lithium is transferred to the
2p5 orbital of fluorine. The lithium atom gives up an electron to form the
positively charged lithium cation with 1s2, 2s0 configuration, and the fluorine
atom receives an electron to form a fluoride anion with 1s2, 2s2, 2p6
configuration.
Thus, the outer energy levels of both ions are completely filled. The ions are held
together by the electrostatic attraction of the positive and negative ions.
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Li + F Li + + F-
1 s2 1 s2 1 s2 1 s2
2 s1 2 s 2 2 p5 2 s0 2 s22 p6
Covalent Bond
A covalent bond is formed by a sharing of two electrons by two atoms.
A hydrogen atom possessing the 1s1 electron joins with another hydrogen atom
with its 1s1 configuration. The two atoms form a covalent bond with two electrons
by sharing their electrons.
H + H H H
In hydrogen fluoride, HF, the hydrogen 1s-electron is shared with a 2p5 electron in
fluorine (1s2, 2s2, 2p5), and the molecule is now held together by a covalent bond.
In this case, the fluorine atom is much more electronegative than the hydrogen
atom and the electrons in the bond tend to stay closer to the fluorine atom. This
is called a polar covalent bond, and the atoms possess a small partial charge
denoted by the Greek (ᵟ) symbol
1s1 2s2 2p5 eight outer

electrons two shared
six non-bonding
+ -
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F H F
H
ᵟ ᵟ
H F Polar Covalent Bond
1.3 BONDING IN CARBON COMPOUNDS
The property of carbon that makes it unique is its ability to form bonds with itself
and therefore allows a large number of organic chemicals with many diverse
properties. Carbon has the property of forming single, double and triple bonds
with itself and with other atoms. This multiple bond ability allows carbon
compounds to have a variety of shapes. In all carbon compounds, carbon forms
four bonds. The types of bonds used by the carbon atom are known as sigma (σ)
and pi (∏) bonds. Different combinations of these bonds lead to carbon single
bonds, double bonds and triple bonds.
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1.3a The Carbon-Hydrogen Single Bond-The Sigma (σ) Bond
By far, most of the bonds in carbon compounds are covalent bonds found
commonly in the carbon-hydrogen single bond. In carbon (1s2, 2s2, 2p2) one of the
electrons of the 2s2 orbital is promoted to the third 2p0 orbital. The s and three p
orbitals hybridize to form four new orbitals of equal energy called sp3 hybrid
orbitals. The electrons in the four sp3 hybridized orbitals bond by overlap with the
1s1 hydrogen orbital. The single covalent bond is called a sigma ( ) bond. The sp3
bonds arrange themselves as far from each other as possible, the shape of a
molecule of methane, CH4, is tetrahedral with 109.50 bond angles.
CARBON - sp3 HYBRIDIZED

2 3
2p 2p
2
Promote 1s to 2p
C
mix all orbitals
1s2 1
1s equal energy
3
Four equivalent sp
Hybridized Orbitals
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The unique property of carbon that differentiates it from the other elements and
allows the formation of so many different organic compounds is the ability of
carbon to bond with itself through covalent bonding. Thus, addition of another
carbon atom to methane results in ethane which has covalent sigma bonds to the
hydrogen atoms and a covalent sigma bond between the carbon atoms. Addition
of more carbon atoms leads to many more compounds.
1.3b The Carbon-Carbon Double Bond-The Pi (∏) Bond
Carbon forms a wide variety of compounds that contain carbon bonded to

another carbon with a double bond between the two atoms. These compounds
are classified as alkenes (older naming calls them olefins). The orbital model
below explains the carbon-carbon double bond. The carbon electron
configuration shows one s- electron being promoted to a p- orbital. But now only
three orbitals are mixed, a s- orbital and two p- orbital, that are called sp2 hybrid
orbitals and are used to form single bonds (sigma bonds). The p- orbital contains
one electron.
The combination of two of the sp2 hybridized carbon atom leads to two carbon
atoms being joined by overlap of sp2 orbitals to form a C-C single bond, and the
side-to-side overlap of the p orbitals to form another bond known as a pi (∏)
bond. In the molecule of ethene shown below there are a total of 5 sigma bonds
and one pi bond. As a result of the bonding in an ethene, the molecule is planar
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with bond angles of 1200 and a C=C bond length that is longer than the C-H bond
length.
CARBON – sp2 HYBRIDIZED

2 3
2p 2p
2
Promote 1s to 2p
mix the !s with the
2 1
1s 1s two of the 2p
leave one p
unhybridized
2p
2
three sp hybridized orbitals
When carbon forms a bond with an electronegative atom such as oxygen,

nitrogen, sulfur or a halogen, the bond is a polar covalent bond with the electrons
of the bond residing closer to the electronegative atom.
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1.3c The Carbon-Carbon Triple Bond
Another type of bond that carbon forms with itself is the triple bond found in a
class of compounds called alkynes. After promotion of the 2s electron to a 2p
orbital, one s- orbital mixes with one p- orbital to give two hybrid sp- orbitals. The
two remaining p- orbitals are used to make p bonds. Thus the carbon is bound by
a sigma bond to hydrogen from one of the sp- hybrid orbital, to the other carbon
atom by a sigma bond from one of the sp- hybrid orbitals, and the two carbon
atoms are bound by two pi bonds from side-to-side overlap of the two p orbitals.
The sp- hybrid orbitals position themselves 180o apart and thus a molecule of
ethyne is linear with the hydrogen atoms 1800 apart.
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CARBON – sp HYBRIDIZED
2 3
2p 2p
2
Promote 1s to 2p
mix the !s with
2 1
1s 1s one of the 2p
leave two p
unhybridized
2p
2
two sp hybridized orbitals
1800
H C C H
Two ∏ bonds, One σ bond ethyne
1.3d Polar Covalent Bonds in Carbon
Carbon forms single, double and triple bonds with elements other than carbon.
The atoms involved in the bonding are usually oxygen, nitrogen, sulfur and the
halogens. These elements are more electronegative than carbon and thus attract
the electrons to themselves. The bonds are therefore polar covalent bonds.
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Bonds that contain a separation of charge possess a dipole moment, a property

that contributes to the overall polarity of the molecule.
1.3e Hydrogen Bonds and Bond Polarity
The bonds O-H, N-H and F-H are highly polar covalent bonds because the
electronegative draws electrons away from the hydrogen atom. In every case the
hydrogen atom has a partial positive charge.
A result of molecules having these highly polarized bonds with the hydrogen atom
partly positive in nature, the hydrogen atom is attracted to the basic site in other
molecules, such as the non-bonding electrons on oxygen and nitrogen
(nonbonding electrons are electrons belong to an element that complete the
octet but do not participate in bonding). This attraction is called hydrogen
bonding and is useful for explaining high boiling points and high melting points of
fairly low mass molecules.
Thus, hydrogen bonding in water explains why the compound with only three
atoms boils relatively high when compared with other molecules of similar mass.
Extra energy is required to break the hydrogen bonds during the boiling process.
In organic compounds hydrogen bonding is very important for describing the

boiling and solubility characteristics of alcohols and acids, and the concept will be
given in more detail in chapters dealing with those types of molecules.
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1.4 ORGANIC STRUCTURES

At first the study of organic chemistry involves understanding the energy and
shapes of simple organic structures. Then, the study progresses to more
complicated three-dimensional structures and finally to the investigation of
reactions of organic molecules. We use the theories of bonding and the facts
about acidic or basic properties of the molecules to understand the overall picture
of what is happening. But the overall goal is to improve mankind through the
development of new and better processes to be applied in medicine, agriculture
and biomedical science, that is, to make life better. Thus we must be able to study
difficult molecules too.
As you proceed through organic chemistry you will write many different
structures, and the writing gets easier with practice. But in the beginning it can be
confusing. Always remember that carbon has four bonds! In writing, an alkane
such as pentane which has five carbon atoms. We could write it by just showing
carbon atoms, but it does not show carbon with four bonds. More correctly it
needs all of its hydrogen atoms, but writing all the hydrogen atoms for
compounds becomes cumbersome. Thus we write condensed structures as shown
below. With some experience, we can write pentane as the line structure with the
ends and the points representing carbon atoms, and we know that the hydrogens
are there without writing them.
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Carbon compounds also exist in rings, called cyclic compounds. Below is the
compound called cyclohexane written several different ways. Even in the most
condensed structures you must realize that all the carbon atoms and all the
hydrogen atoms are present even though the C's and H's are not written. These
shorthand methods of writing structures are very helpful in speeding up the
writing of equations, and thus understanding them is necessary.
The structures of organic chemicals can be very complicated and very interesting.
Sometimes, they are so complex that condensed structures are the only
reasonable presentation. But as always, the carbon atom has four bonds. Several
advanced organic structures are shown below.
1.5 CLASSIFICATION OF ORGANIC COMPOUNDS
Organic compounds are often classified according to the type (s) of functional
groups present. These functional groups are presented in detail in the remaining
chapters. The on-sight recognition of functional groups is required for an
adequate study of organic chemistry.
1.6 SUMMARY
The science of Organic Chemistry has a broad and diverse past with many
investigators from many countries making discoveries that when combined over
200 years led to the field of Organic Chemistry. The intrigue found with
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substances that contain carbon, organic compounds, arose because so many

different substances could be found in nature and many of them had medicinal
uses. The discovery of a laboratory synthesis of urea by Frederich Wöhler (1828)
showed that organic chemicals did not have to be prepared by the vital forces of
nature but could also be prepared by humans, thus opening the way for the field
of synthetic organic chemistry.
The theory of bonding in chemicals achieved prominence because of the

contributions by Heisenberg and Schroedinger, and many others. The electronic
configuration of elements is seen as combination of electrons in specific energy
levels called shells that further contain energy levels known as subshellswith s, p,
d and f orbitals. The ability of the elements to donate or share their electrons
with other elements to form bonds is the basis for the formation of all
compounds. When the elements form bonds by complete donation of acceptance
of electrons the bonds form are called ionic bonds. Bonds in compounds that are
formed from the sharing of two electrons are called covalent bonds, and
constitute the majority of bonds found in organic compounds. Carbon compounds
contain the carbon atom in several hybridized states. The theory of hybridization,
meaning that the electronic configuration of carbon is altered when it forms
bonds, is required to explain the shapes and properties of organic compounds.
Thus carbon is said to be hybridized in sp3, sp2, and sp electronic configurations
that give rise to carbon single bonds called sigma (σ) bonds. The unhybridized p
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orbital in the sp2 and sp configurations is used to form bonds called pi (∏) bonds,
that give rise to the double and triple bonds found in ethenes and ethynes
respectively. The bonds from carbon to polar atoms are often polar and are called
polar covalent bonds.
Carbon compounds that contain OH and NH bonds give rise to hydrogen bonding,
much like that found in water, and lead to a number of interesting chemical and
physical properties.
The writing of chemical structures is extremely important in the study and

practice of organic chemistry. Of utmost importance is that when one writes or
draws a structure another person can understand the structure. Thus neatness is
required. Many computer programs are available to assist with the writing of
chemical structures. Organic structures can be written to show the complete
structure with all the elements and bonds, but often this is too cumbersome. Thus
various types of condensed structures can be written with the ultimate
condensed structures written only with lines and an understanding of where the
carbon and hydrogen atoms are located.
Carbon combines with many elements and itself to form a very wide variety of
substances. These substances are classified according to the exact type of
substituent and bonding on the carbon atom. The study of organic chemistry is
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often conducted by studying the individual classes of compounds as will be seen

in the following chapters.
1.7 PROBLEM SET
1.1 A famous scientist of the 20th century was Linus Pauling who received two
Nobel prizes during his life. Look up a biography of Pauling and list his most
notable contributions to science.
1.2 Sections 1.2a shows the electronic configuration for the 2nd row elements.
Show the electronic configuration for the third row elements. Common ions
in the 3rd row are Na+1, Mg+2, Al+3, Si+4, P+5, S-2, Cl-1. What characteristics of
their electronic configurations do these ions share that accounts for their
stability?
1.3 The dipole moment (m) of a molecule is the vector sum of the dipole
moments of the individual bonds. In some cases these sums cancel each
other while in other cases they enhance each other. Given the bond
moments of H-C (0.4) and C-Cl. (1.5), predict the dipole moment, and thus
the polarity, of CH3Cl, CH2Cl2, CHCl3 and CCl4.
1.4 For the compounds below write the complete structure and designate the
bonding in each bond.
1.5 Hydrogen bonds in alcohols and carboxylic acids have a bond strength of 810
kcal/mole. The energy required to break these bonds explains the higher by
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of hydrogen bonded substances. a) Use a chemical handbook to find the

boiling points of the following compounds to see the effect of hydrogen
bonding on the boiling point.
CH3CH2OCH2CH3 versus CH3CH2CH2CH2OH versus CH3CH2COOH
b) What are the molecular weights for these compounds and how does the
molecular weight affect the bp in them?
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CHAPTER TWO
2.0 THE RELATIVE IMPORTANCE OF DIFFERENT ELEMENTS
From an academic point of view, all elements might be said to be equally
important. The chemistry of each has to be understood in detail if the chemistry
of matter as a whole is to be understood in detail. From the point of view of the
world at large, however, the relative importance of different elements varies
widely, and some elements are little more that chemical curiosities. In a university
course of inorganic chemistry, a balance has to be struck between a uniform
treatment of all of the elements, and a greater concentration on the socially more
important ones.
The question of, ‘which are the socially more important elements’, is to some
extent, a matter of opinion. A chemist working in the plastics industry would
doubtless come up with a different list from one working in the metals industry,
and someone working with agricultural chemicals would doubtless have different
ideas from someone working on ceramics. Most people would agree, however,
that among the most important elements are:
(i) The more abundant elements,

(ii) Elements that are consumed on a very large scale, and
(iii) Elements that are actively sought for despite very poor resources. Data on
each of these categories are presented below.
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2.1 THE RELATIVE ABUNDANCE OF DIFFERENT ELEMENTS

The figures below give the relative abundance of different elements in the
atmosphere, the hydrosphere, the lithosphere, and the biosphere. The figures are
necessarily approximate, and slightly different values may be found in other
places. The percentages are percentages by mass - the percentage numbers of
atoms would of course be different. All abundances over 0.1% have been
included. The figures reveal that some 99% of the matter in the world around us is
made up of as few as 14 elements. Note, however, that many of the remaining
elements in the biosphere, despite their low concentration, are essential to its
healthy continuance.
Atmosphere
Nitrogen 75.5%
Oxygen 23.0%
Argon 1.4%
Total 99.9%
Hydrosphere
Oxygen 85.8%
Hydrogen 10.7%
Chlorine 2.1%
Sodium 1.1%
Total 99.7%
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Lithosphere
Oxygen 46.6%
Silicon 27.7%
Aluminum 8.1%
Iron 5.0%
Calcium 3.6%
Sodium 2.8%
Potassium 2.6%
Magnesium 2.1%
Titanium 0.4%
Total 98.9%
Biosphere
Oxygen 52.4%
Carbon 39.4%
Hydrogen 6.6%
Nitrogen 0.5%
Calcium 0.4%
Potassium 0.2%
Total 99.5%
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2.2 THE RELATIVE CONSUMPTION OF DIFFERENT ELEMENTS

The figures below give the annual world consumption of different elements, as
elements and compounds, in millions of tons. The figures vary from year to year
and are necessarily approximate. Siliceous materials and limestone used for
building purposes have been excluded, and a lower limit has been set at 0.1
million tons.
Millions of tons per year
Carbon 1000-10000
Iron, sodium 100-1000
Calcium, nitrogen, oxygen, potassium, sulfur 10-100
1-10
Aluminium, barium, chlorine, chromium, copper,
fluorine, hydrogen, lead, magnesium, manganese,
phosphorus, zinc
Boron, nickel, tin, titanium, zirconium 0.1-1

Of the 25 elements in the table, 10 are very plentiful, and appear in the first three
tables of the previous section (2.1). Of the remainder, the majority occur in
relatively concentrated deposits, from which they or their compounds can be
extracted fairly easily (e.g. hydrocarbons from petroleum). For copper, lead, zinc,
nickel, and tin, demand is such that less concentrated deposits have to be
worked, down to 0.5% in the case of copper and 0.2% in the case of tin (see
below).
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2.3 ELEMENTS SOUGHT AFTER FROM VERY LOW-GRADE ORES

The following table gives the minimum metal content that an ore must have
before it can be mined and smelted economically with present-day technology.
Values are given up to a limit of 0.5%, and may be compared with the value for
iron of 25%.
Platinum 0.0003%
Gold 0.001%
Silver 0.01%
Uranium 0.2%
Mercury 0.2%
Tin 0.2%
Molybdenum 0.3%
Copper 0.5%
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CHAPTER THREE
3.0 CLASSIFICATION OF ELEMENTS INTO METALS AND NON-METALS
3.1 TYPES OF ELEMENT
The classification of elements into metals and nonmetals, with the intermediate
category of semimetal, is a fundamental one in inorganic chemistry.
Metallic elements are characterized by the following properties under ordinary

conditions:
(i) high lustre, high opacity over the visible spectrum;

(ii) high electrical and thermal conductivity.
Non-metals are characterized by:

(i) no lustre, high transparency over the visible spectrum;
(ii) low electrical and thermal conductivity.
Semi-metals are characterized by:

(i) high opacity over the visible spectrum, little or no lustre;
(ii) intermediate electrical conductivity.
Notes
(1) “High opacity over the visible spectrum” is a way of saying that the
substance absorbs light strongly over the whole range of the visible spectrum, or
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at least over the whole range beyond the red. If it is not lustrous, therefore, the
substance appears black to the eye, or very dark brown.
“High transparency over the visible spectrum” is a way of saying that the
substance absorbs light weakly over the greater part of the visible spectrum, if
not over all of it. If no light is absorbed, the substance appears colourless or
white. (Colourless substances look white when finely divided because light is
scattered from the many crystal faces. Similarly, coloured substances become
paler on grinding.) If some light is absorbed, the substance appears coloured, the
colour being the complementary one to the colour of the light that is absorbed.
The complementary colours to the main spectral colours (red, orange, yellow,
green, blue, and violet) are obtained by writing the colours in order round a circle.
Those appearing opposite each other are complementary.
(2) `It is possible to be more quantitative about the distinction in electrical

conductivity. Electrical conductivity (k) is defined as the reciprocal of the
resistivity, ṗ.
k = 1/ṗThe
resistivity is defined by the equation
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R = ṗ (1/A)
where, R is the resistance of a uniform conductor,

l is its length, and
A is its cross sectional area. The SI unit of k is ohm meter Ωm, and its value
is equal to the resistance that a meter cube of the substance offers to the
passage of electricity from one parallel face to another. The SI unit of k is
thus Ω-1m-1.
On the basis of their ability to transmit an electric current, materials can be

divided into four main classes:
Ordinary conductors, characterized by having conductivities greater than about at
room temperature, which fall with increase of temperature.
Semi-conductors, characterized by having conductivities between about and at

room temperature, which rise with increase of temperature, and are highly
sensitive to traces of impurity.
Electrolytic conductors, characterized by the chemical decomposition that takes

place at the points at which a direct current enters and leaves the material. (The
words “electrolysis”, “electrolyte”, “electrolytic”, come from the Greek lyo,
loosen).
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Insulators, characterized by conductivities of less than about at room

temperature, rising with increase in temperature.
In these terms, metals are conductors, semimetals are semiconductors, and

nonmetals are insulators.
(3) It is necessary to specify “under ordinary conditions” because, under extreme

conditions, the character of a substance can change profoundly. Thus:
(i) gases at very low pressures become good conductors of electricity, as in a

discharge tube at low pressure;
(ii) metals at high temperatures vaporize, and lose their metallic properties
completely (e.g. mercury boils at 357 ºC to give a colourless vapour, which
is a poor conductor of electricity at ordinary pressures);
(iii) semi-metals and nonmetals at very high pressures become metallic in
character (e.g. at 150 atmospheres iodine becomes a very good conductor
of electricity).
(4) A further characteristic of metals that is usually given is that, in the solid state,
they are malleable (easily hammered into sheets) and ductile (easily drawn into
wires). By contrast, nonmetals in the solid state are brittle and easily powdered.
In practice, however, while the majority of elements that are metallic according to
the above criteria are indeed malleable and ductile, there are a few that do not
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have this property, even when ultrapure. (Slight traces of impurity can produce
brittleness in metals. Thus, ordinary commercial tungsten is so brittle that it can
only be worked with difficulty, whereas the ultra-pure metal can be cut with a
hacksaw, turned, drawn, or extruded.) Since the exceptional elements include
some whose metallicity has never been questioned - e.g. manganese, cobalt, and
zinc - it seems better not to make malleability and ductility a characteristic of
metals, but rather a property possessed by most of them.
Zinc is a particularly interesting case, because it is malleable at some

temperatures and brittle at others. Thus, it is brittle at room temperature, but
softens above 1000C. At 2050C, however, it becomes brittle again, and can then be
powdered in a mortar.
3.2 ASSIGNMENT OF ELEMENTS TO CLASSES
In most cases, this is straightforward.

The clear-cut nonmetals are: hydrogen, nitrogen, oxygen, fluorine, sulfur,
chlorine, bromine, and the inert or noble gases (helium, neon, argon, krypton,
xenon).
The clear-cut semimetals are boron, silicon, germanium, and tellurium.
The clear-cut metals constitute all of the remaining elements, with the exception
of the problem cases discussed below.
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PROBLEM CASES
Carbon: Under ordinary conditions, carbon exists in two common forms, graphite
and diamond, of which graphite is the more stable. Diamond is definitely
nonmetallic, but graphite has properties on the borderline between a semimetal
and a metal. Thus, it is a shiny, black solid, readily separated into flakes, with a
metallic conductivity in the plane of the flakes, and a semi-metallic conductivity
perpendicular to the plane. Other forms include black, petrol-soluble “fullerenes”.
When pure, these are insulators.
Phosphorus: This exists in a number of different forms: one white, several red,
and several black. The white form can be made by condensing the vapour. It melts
at 44°C and boils at 280°C. A red form is obtained when the white form is heated
to just below its boiling point. A black form can be obtained by heating the white
form under a very high pressure, or in the presence of a mercury catalyst. The
yellow and red forms are insulators; the black forms are semiconductors. The
most stable form under ordinary conditions is black; all forms, however, melt to a
colourless liquid.
Arsenic: This can be obtained in several forms, ranging from a yellow one, which is
similar to white phosphorus, to a grey one, which is a metal. The metallic form is
the most stable under ordinary conditions; the yellow one is very unstable.
32
Antimony: This can also be obtained in several forms, ranging from yellow to
metallic. The metallic form is again the most stable, with the yellow very unstable.
Selenium: This exists in three red forms, one black form, and one grey. The red
and black forms are insulators; the grey is a semiconductor. The latter is the most
stable.
Iodine: Iodine crystallizes in blackish-grey opaque scales, with an almost metallic

lustre. In the plane of the scales, it has the conductivity of a semiconductor;
perpendicular to the plane it is an insulator.
3.3 VOLATILITIES OF METALS AND NON-METALS
The volatility of a substance is the ease with which the substance is vaporized. It is
conveniently measured by the temperature at which the substance boils or
sublimes at atmospheric pressure. A broad generalization concerning the relative
volatilities of metals and nonmetals is the following:
Metals are generally involatile, i.e. they have boiling points in excess of 5000C.
Only mercury has a boiling point below 5000C, this being at 3570C. Most metals
have their boiling point somewhere between 10000C and 40000C. The highest
value is for tungsten, at 56600C.
33
Non-metals vary from being very volatile to very involatile. All the definite
nonmetals listed above have boiling points below 5000C, and most are gases at
room temperature. The least volatile is sulfur, boiling at 445 ºC. If, however, we
include carbon among the nonmetals, as surely we should, this lies at the
opposite extreme of volatility, boiling at 48300C.
3.4 CHEMICAL PROPERTIES OF METALS AND NON-METALS
There are many chemical differences between metals and nonmetals. These will
become apparent in the following chapters.
Some elements have very similar properties and are grouped into families. These
include:
Alkali metals: Li, Na, K, Rb, Cs
Alkaline earth metals: (Mg,) Ca, Sr, Ba
Halogens: F, Cl, Br, I
Inert or noble gases: He, Ne, Ar, Kr, Xe
“Alkali” is an Arabic word meaning “the ash” (ash from plants contains sodium
and potassium carbonates). “Halogen” means “producer-of (-gen) salt (Greek
34
hals)”. Some chemists class magnesium as an alkaline earth metal as it is quite

similar to calcium, often occurring with it in nature.
The gases He, Ne, Ar, Kr, and Xe were called “inert” when they were thought to
be completely inactive.
Their name was changed to “noble” after the xenon fluorides were discovered in
1962. This was because metals having a low activity (but nevertheless some
activity) like gold and platinum are sometimes called “noble” as they are used for
noble purposes. The change was inept. “Inert” need not imply complete inactivity,
and “noble” is hardly apt (commoners breathe in these gases no less than nobles
do!).
Other families will be discussed in a later chapter.
35
CHAPTER FOUR
4.0 TYPES OF FORMULA
4.1 EMPIRICAL FORMULAE
The empirical formula of a compound is the simplest possible formula indicating

the relative numbers of different atoms in it. The formula is determined from the
composition of the compound.
Examples: ethane, CH3 salt, NaCl
4.2 MOLECULAR FORMULAE
The molecular formula of a compound indicates the total numbers of different

atoms in a molecule of it. For molecular compounds, the molecular formula is
determined from the empirical formula and the molecular mass of the compound.
For non-molecular compounds, it is set at the empirical formula multiplied by
infinity, representing a very large number.
Examples: C2H6 (NaCl)8
In practice, a mixture of empirical and molecular formulae are used - NaCl

alongside C2H6. Even hybrid formulae are used, e.g. Na2O2 (as this compound
contains O22- ions). Ideally, the different formulae should be distinguished, e.g.
with brackets:
36
(NaCl) [C2H6] (Na2[O2])
In practice, we have to be able to tell one from the other.
4.3 STRUCTURAL FORMULAE
The structural formula of a compound indicates the way in which the atoms are
united in the molecule. There are two main types: (i) constitutional formulae, (ii)
descriptive formulae.
(i) Constitutional formulae
(a) Covalent compounds: bond formulae
These are determined from the valencies of the atoms (Chap. 8) and such
structural information as is required.
(b) Ionic compounds: ion formulae
These are determined from the charges on the ions.

Example: Na+Cl–
(ii) Descriptive formulae
These do not attempt to give any indication of the bonding.

(a) Single stroke formulae
These are formulae in which bonded atoms are connected up with a single
stroke, with no indication of bond number or polarity. They are usually
37
used for compounds in which the bonds have an intermediate bond

number or polarity (Chaps. 7 and 8). An example is the following
representation of one layer of graphite:
This kind of representation is also used in referring to bond distances in a

compound, as in the statement “the C–C bond length in graphite is 1.42 Å”. Care
needs to be taken not to confuse formulae of this kind with bond formulae [(i)(a)
above].
(b) Descriptive formulae of crystals
If the crystal structure of a non-molecular compound is known, the arrangement

of atoms can be represented in the form [ABx/y]., or more generally [ABx/yBx/y.…].,
where x is the number of nearest neighbours B to A, and y is the number of
nearest neighbours A to B - 1/y being the share atom A has of each neighbouring
atom B (Chap. 5).
Example: [NaCl6/6]
This indicates that, in crystalline sodium chloride, each sodium atom (ion) is
surrounded by six chlorine atoms (ions), each of which is shared between six
sodium atoms (ions), giving an empirical formula NaCl. Crystallographers call the
number of nearest neighbours the “coordination number”.
38
4.4 GEOMETRICAL FORMULAE
The geometrical formula of a compound represents the geometrical arrangement

of the atoms in the molecule. It is determined from the structure of the
compound. To represent the geometry properly really requires a
threedimensional model, but we have to try to do this in two dimensions.
39

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2, Tokunbo Alli Street, Ikeja Lagos

E-mail: inquiries@jptsonline.org, chrisafety@jptsng.org

Tel: 01- 3427217, 08132733378

Scientists believed (Berzelius, 1807) that organic chemicals found in nature

therefore, it would be impossible to accomplish a laboratory synthesis of the

Organic chemistry developed into a productive and exciting science in the

1.2 THE CHEMICAL BOND

1.2a Atomic Theory

Shell s p d f Total Electrons Possible

*energy level 1 contains up to two electrons in a spherical orbital called a 1s-

*energy level 4 contains up to thirty-two electrons, two electrons in a 4s-orbital,

Element (atomic number) Electron Configuration

H (1) 1s1 (1st shell, s orbital, one electron)

1.2b Electro negativity

Electronegativity is the ability of an atom to attract electrons to itself, and

Electronegativity also increases as we go from the bottom to the top of a column

electronegative I < Br < Cl < F electronegative

Ionic bonding is important between atoms of vastly different electronegativity.

A covalent bond is formed by a sharing of two electrons by two atoms.

1s1 2s2 2p5 eight outer

H F Polar Covalent Bond

1.3 BONDING IN CARBON COMPOUNDS

1.3a The Carbon-Hydrogen Single Bond-The Sigma (σ) Bond

CARBON - sp3 HYBRIDIZED

1.3b The Carbon-Carbon Double Bond-The Pi (∏) Bond

Carbon forms a wide variety of compounds that contain carbon bonded to

CARBON – sp2 HYBRIDIZED

When carbon forms a bond with an electronegative atom such as oxygen,

1.3c The Carbon-Carbon Triple Bond

Two ∏ bonds, One σ bond ethyne

1.3d Polar Covalent Bonds in Carbon

Bonds that contain a separation of charge possess a dipole moment, a property

1.3e Hydrogen Bonds and Bond Polarity

In organic compounds hydrogen bonding is very important for describing the

1.4 ORGANIC STRUCTURES

1.5 CLASSIFICATION OF ORGANIC COMPOUNDS

substances that contain carbon, organic compounds, arose because so many

The theory of bonding in chemicals achieved prominence because of the

The writing of chemical structures is extremely important in the study and

often conducted by studying the individual classes of compounds as will be seen

1.7 PROBLEM SET

of hydrogen bonded substances. a) Use a chemical handbook to find the

CH3CH2OCH2CH3 versus CH3CH2CH2CH2OH versus CH3CH2COOH

(i) The more abundant elements,

2.1 THE RELATIVE ABUNDANCE OF DIFFERENT ELEMENTS

2.2 THE RELATIVE CONSUMPTION OF DIFFERENT ELEMENTS

Millions of tons per year

Iron, sodium 100-1000

Calcium, nitrogen, oxygen, potassium, sulfur 10-100

Boron, nickel, tin, titanium, zirconium 0.1-1

2.3 ELEMENTS SOUGHT AFTER FROM VERY LOW-GRADE ORES

Metallic elements are characterized by the following properties under ordinary

(i) high lustre, high opacity over the visible spectrum;

Non-metals are characterized by:

Semi-metals are characterized by:

(2) `It is possible to be more quantitative about the distinction in electrical

resistivity is defined by the equation

where, R is the resistance of a uniform conductor,

On the basis of their ability to transmit an electric current, materials can be

Semi-conductors, characterized by having conductivities between about and at